Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic

Definitions

• This invention relates to distillate petroleum products containing additives which improve the temperature-viscosity properties, including low-temperature flowability, cold-flow plugging point, and pour point characteristics, of distillate petroleum products. More particularly, this invention relates to distillate petroleum products having improved low-temperature properties, comprising a distillate fuel and an effective amount of an ethylene-unsaturated, ester-substituted olefin terpolymer at a concentration sufficient to substantially prevent thickening of the petroleum product and crystallization of large wax particles that can clog lines and filters at low temperatures.
• Distillate petroleum products having relatively high pour points have serious cold weather drawbacks. For example, distribution of the distillate by pumping or siphoning is difficult or impossible at temperatures at or near the pour point. Furthermore, in applications such as engines or home burner installations at or near the pour point, the flow of the fuel through filters cannot be maintained, leading to the failure of equipment to operate. At low temperatures large wax particles can form in the fuel and the fuel can become so thickened that transfer of petroleum products through transfer lines from container to container or from container to use is impossible. Commonly, polymeric additives are used to improve the viscosity-temperature properties of the petroleum product.
• Fuels having relatively-high distillation end points are believed to contain a higher proportion of certain heavier n-paraffins or waxy hydrocarbons which cause the fuel to behave in a manner different than fuels with lower distillation end point temperatures, e.g., below about 640°F., in the presence of low temperature-viscosity-improving polymeric additives.
• fuel oil and diesel oil produced in European refineries commonly have compositions different than comparable diesel and fuel oils produced in the United States.
• Cold-flow-improving polymers optimized for performance in domestic American fuels commonly do not produce equivalent improvement in the cold-flow characteristics in European fuels. The trend in production of domestic American fuels is to increase the distillation end point temperature to increase the yields of fuel.
• distillates derived from naphthenic crude oil generally have substantially different proportions of wax and other heavy hydrocarbons than found in distillates derived from aromatic or paraffinic crudes.
• polymeric materials that improve the flowability of distillates often do not improve the plug point characteristics of the distillate.
• Ethylene-based polymers effective as pour point depressants, low-temperature-flowability improvers or as cold-flow plugging point improvers in distillate fuels include ethylene-vinyl acetate, ethylene-acrylate, ethylene-methacrylate, hydrolyzed ethylene-vinyl acetate, ethylene-alpha olefin, ethylene-vinyl fatty acid, ethylene-dialkylvinylcarbinol, etc.
• Ethylene-based terpolymers including ethylene and two or more other monomers include ethylene-styrene-acrylate and methacrylate; ethylene-styrene-vinylcar- binol; ethylene-vinyl acetate-unsaturated fatty acid; and ethylene-vinyl acetate-dialkyl maleate.
• ethylene-based. copolymers containing alpha-olefins having 3-22 or more carbon atoms include ethylene-based. copolymers containing alpha-olefins having 3-22 or more carbon atoms.
• ethylene-alpha-olefin copolymers are found in Cohen, U.S. Patent No. 3,958,552, which discloses ethylene-alpha-monoolefin copolymers wherein the monoolefin has 10 to 22 carbon atoms; Bur- kard, U.S. Patent No. 3,645,704, which discloses halogenated copolymers comprising ethylene and C 3 -C 6 alpha-olefins; Ilnickyj, U.S. Patent No.
• copolymers and terpolymers discussed above suffer the disadvantage that they provide either limited cold flow improvement in distillates or heavy hydrocarbons such as crudes, heavy gas oils, and synthetic oils, or that the copolymers and terpolymers fail to give economically significant cold-flow-improving properties to distillate fuels derived from different crude oils having distillation end point temperatures below about 640°F. or distillation end point temperatures greater than 640°F.
• polymeric additives which effectively reduce the pour point and cold flow plugging point of fuels of different boiling ranges and compositions and which have the highest activity in each fuel are desired. Additives appear to prevent low-temperature flow problems and to. inhibit wax crystal formation by a mechanism in which the polymeric additive, with a polymethylene backbone and various side chains, is absorbed onto a growing wax crystal surface. A portion of the polymeric side chain resembles the crystal structure to the extent that the polymer is absorbed and bound to the crystal surface. Other side chains are dissimilar to the crystal structure preventing further growth of the crystal by blocking the absorption of additional wax molecules. In other words, additional wax molecules no longer fit the crystal surface altered by the shape and position of the polymer side chains. The wax crystals are thereby kept very small and, as such, do not cause low-temperature-flowability problems.
• the principal object of this invention is to economically prevent thickening of distillates and crystallization of wax particles in distillates at low temperatures by the addition of highly effective novel polymeric additive compositions at low concentrations.
• Another object of this invention is to provide polymeric additives providing anti-crystallization and anti-thickening activity at low concentrations to a variety of distillate fuels having various compositions and boiling ranges.
• a further object of this invention is to improve the low-temperature flowability, cold-flow plugging point, and pour point of a variety of distillates with a polymeric additive. Further objects appear hereinafter.
• the polymer chains tend to be coiled and reduced in size.
• the polymer chains tend to be elongated.
• the polymers tend to be more effective in preventing crystal growth in a greater area on each wax crystal.
• the greater elongation of-the polymer chains both produces an increase in the effectiveness of each polymer chain and permits a reduction in the concentration of the polymer producing improved low-temperature flowability properties.
• the polymeric flow improvers of this invention comprise ethylene-unsaturated, ester-substituted olefin terpolymer.
• Substituted olefins useful in producing the ethylene-unsaturated, ester-substituted olefin terpolymer of this invention have the characteristic that at least one unsaturated carbon has two substituents having the following general formula: wherein each R is independently selected from substantially alkyl or substantially aryl groups and each R 1 is independently selected from hydrogen or R.
• the olefin substituents comprise substantially hydrocarbyl or alkyl groups containing saturated or unsaturated carbon atoms.
• alkyl substituents examples include methyl, ethyl, isopropyl, tertiary butyl, 1,1,3-trimethylbutyl, 2-ethylhexyl, 1,3,5,7,9-peatamethyldecyl, 2,2-methylbutyl, 2,2,4,4-tetramethylpentyl, tertiary eicosyl and n-eicosyl.
• unsaturated substituents such as vinyl, 1-methylvinyl, 2-methylvinyl, 2-butenyl, cyclohexenyl, methylcyclohexenyl, or eicosenyl.
• Examples of useful substituted olefins include isobutylene (2-methyl propene), 2-ethyl-propene, 2-isobutyl-l-butene, 1,3-butadiene, 2-n-butyl-pentene, 2-methyl-1-octene, 3-ethyl-2-octene, 3-t-butyl-2-hexene, etc.
• the substituted olefin comprises isobutylene (2-methyl-l-propene), or isobutylene oligomers, including diisobutylene isomers (2,4,4-trimethyl-l-pentene or 2,4,4-trimethyl-2-pentene or mixtures thereof), triisobutylene isomers (2,4,4,6,6-pentamethyl-1-heptene, 2,4,4,6,6-pentamethyl-2-heptene, cis- and trans-2,2,4,6,6-pentamethyl-3-heptene, or 2-neopentyl-4-4-dimethyl-l-pentene or mixtures thereof), tetraisobutylene isomers, etc.
• Substituted olefins such as oligomers of isobutylene containing more than about 10 carbon atoms in the substituent, can be used, but with somewhat poorer performance due to steric effects reducing the polymerization rate and polymer molecular weight.
• Unsaturated esters polymerizable with ethylene and the substituted olefins include unsaturated mono- and diesters of the general formula: wherein R 3 is hydrogen or methyl; R 4 is a -OOCR 6 or -COOR6 group wherein R 6 is a hydrogen or a C 1 to C 16 , preferably a C l to C 4 straight or branched chain alkyl group; and R 5 is hydrogen or a -COOR 6 .
• the monomer when R 3 and R 5 are hydrogen and R 4 is -OOCR 6 , includes vinyl alcohol esters of C 2 to C 17 monocarboxylic acids, preferably C 2 to C 5 monocarboxylic acids including vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, etc.
• R 4 is -COOR 6' such esters include methylacrylate, methyl methacrylate, lauryl acrylate, palmityl acrylate, palmityl methacrylate, and C 13 oxo alcohol esters of methyacrylic acid.
• Examples of monomers where R 3 is hydrogen and R 4 and R 5 are -COOR 4 groups include mono- and diesters of unsaturated dicarboxylic acid such as mono-C 3 -oxofumarate, di-C 13 -oxofumarate, diisopropylmaleate, dilaurylfumarate, ethylmethylfumarate, etc.
• the unsaturated ester comprises vinylacetate, alkylacrylate, alkylmethacrylate, and dialkyl fumarate wherein the alkyl groups are straight or branched chain and have 2-17 carbon atoms.
• polymers with side chains that resemble wax crystal structures and at the same time have side chains which are dissimilar to wax crystals are desired.
• the dissimilar side chains provided by the unsaturated esters present in the molecule poison the crystal growth.
• the ethylene and substituted olefin moieties in the polymer chain both resemble wax crystals and, at the same time, the bulky substituents on the olefin cause the polymer chain to be elongated and more effective in poisoning crystal growth.
• the polymer disclosed herein contains a critical amount of a substituted olefin which optimizes the cold flow properties. Polymers of this type, to the best of my knowledge, are not disclosed elsewhere.
• the unique polymers disclosed herein are polymers which improve the cold-flow properties of petroleum products in a more cost-efficient manner than prior-art terpolymers. Lesser amounts of these novel products than prior-art materials can be used to obtain simultaneously improved pour point, improved low-temperature flowability and improved cold-flow plugging point properties of a variety of fuels from a variety of sources.
• Terpolymer compositions comprising 0.1-10.0 moles or preferably 5.0-10.0 moles of ethylene per mole of unsaturated ester and 10-100 moles or preferably 40.0-70.0 moles of ethylene and unsaturated ester per mole of substituted olefin provide the maximum performance in providing exceptional low temperature-viscosity properties to the distillate.
• the terpolymer can be produced by conventional gas-or liquid- (solvent-) phase polymerization using conventional free-radical polymerization initiators such as benzoyl peroxide, tertiary butyl peroxide, ditertiary butyl peroxide, cumene peroxide, and other free-radical polymerization catalysts well-known in the art.
• the peroxide is used generally in a concentration of about 0.1 to about 10 weight percent and preferably 1 to 2 weight percent; of the monomers.
• a typical hydrocarbon polymerization solvent may be used, for example, benzene, cyclohexane, hexane, toluene, xylene, and other aromatic solvents.
• the polymerization temperature is generally within the range of about 150-350°F. and preferably from about 175-275°F.
• the pressure can be within the range of about 500 to about 3,000 psi absolute or more, preferably 800 to 1,500 psia.
• the polymerization is carried out until the polymerization is complete, generally from about 1 to 12 hours. Conventional gas- or liquid-phase polymerization techniques are used, but the ratios of reactants must be adjusted so that the required content of monomer units in the final product is achieved.
• the molecular weight of the polymer can range from about 500 to 50,000 or more, preferably from about 700 to about 5,000, and more preferably from 800 to about 2,000.
• the terpolymer composition of this invention is an extremely effective pour point depressant.
• the terpolymer is incorporated in the distillate fuel in a sufficient concentration to lower the pour point of the hydrocarbon to a satisfactory degree.
• additives are preferably used in minimum concentrations.
• the additive can be used satisfactorily in difficult-to-treat hydrocarbons in a concentration from about 10 to about 2,500 parts per million based upon the total amount of hydrocarbon.
• the polymer is used in the range of 10 to 500, most preferably 10 to 350, parts per million by weight of the hydrocarbon.
• the distillate fuel oils of this invention boil in a range between 250 and 900°F. and have a cloud point from about 0° to 45°F.
• the fuel oil can comprise straight run or cracked gas oil or a blend in any proportion of straight run or thermally cracked and/or catalytically cracked distillates, etc.
• the most common petroleum middle distillate fuels are kerosene, diesel fuels, jet fuels, and heating oils. A low-temperature-flow problem is most usually encountered with No. 1 and No. 2 diesel fuels and with No. 1 and No. 2 heating oils.
• a typical heating oil specification calls for a 10 percent distillation point no higher than about 440 0 F., a 50 percent distillation point no higher than about 520°F., and a 90 percent distillation point at least 540°F. and no higher than about 640-650°F., although some specifications set the 90 percent distillation point as high as 675°F. or higher. Other minor variations in the distillation points may occur.
• a typical specification for diesel fuels includes a minimum flash point of 100 0 F. and a 90 percent distillation point (ASTM D-110) between 540°F. and 640°F. (see ASTM designations D-496 and D-975). As discussed above, distillate fuels having specifications 50°F. higher than that shown above are being produced in Europe and potentially can be used in the United States.
• the pour point depressant discussed herein can be used in conjunction with other additives normally incorporated in hydrocarbons which will improve other hydrocarbon properties.
• additives include anti-oxidants, corrosion and rust inhibitors, viscosity index improvers, cetane improvers, metal deactivators, dyes, anti-microbial agents, detergents, etc.
• the Cold Flow Plugging Point Test is carried out by the procedure described and detailed in Journal of the Institute of Petroleum, Vol. S2,(NO. 510, June 1966, pp. 173-185. In brief, the Cold Flow Plugging Point Test is carried out with a 45-milliliter sample of the oil to be tested which is cooled in a bath maintained at about -34°C. Upon every one degree drop in temperature starting from 2°C.
• the oil is tested with a test device consisting of a pipette on whose lower end is attached an inverted funnel. Stretched across the mouth of the funnel is a 350-mesh screen having an area of about 0.45 square inch. A vacuum of about 8 inches of water is applied to the upper end of the pipette by means of a vacuum line while the screen is immersed in the oil sample. Oil is drawn by the vacuum through the screen into the pipette to a mark indicating 20 milliliters of oil. The test is repeated at each 1°C. drop in temperature until the clogging of the screen by wax crystals prevents the oil from filling the pipette to the aforesaid mark. The results of the test are reported as the centigrade temperature at which the oil fails to fill the pipette in the prescribed time.
• Example II was repeated, except that the initial reaction pressure was 1,450 psig instead of 1,375 psig and the olefin polymerized in the reaction was 2,4,4-trimethyl-2-pentene (diisobutylene isomer) instead of 2,4,4-trimethyl-l-pentene.
• the polymerization yielded 14.0 grams of polymer.
• Example I was repeated, except that the initial reaction pressure was 1,000 psig instead of 800 psig and the monomer solution contained 56.3 grams (0.65 mole) of vinyl acetate and 3.3 grams (0.29 mole) of a mixture of diisobutylene isomers, instead of 45.0 grams of vinyl acetate and 3.3 grams of isobutylene, in 120 milliliters of cyclohexane. The yield of the polymerization was 36.5 grams.
• Example I was repeated, except that the initial reaction pressure was 1,400 psig instead of 800 psig and the monomer solution contained 10.0 grams (6.059 moles) of a mixture of triisobutylene isomers instead of 3.3 grams of isobutylene. The yield of the polymerization was 22.3 grams.
• Example I was repeated, except that the initial reaction pressure was 1,550 psig instead of 800 psig and the monomer solution contained 56.5 grams of vinyl acetate and 4.25 grams of 2-methyl-4-phenyl-l-butene in 120 milliliters of cyclohexane instead of 45.0 grams of vinyl acetate and 3.3 grams of isobutylene. The yield of the polymerization was 26.7 grams of polymer.
• Table I shows the characterization of the polymer in terms of composition of monomer molecular weight and polydispersion.
• Tables II and III show that the polymers attain excellent improvement in the cold-flow properties of distillate fuels.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

Family

ID=24874835

Family Applications (1)

Country Status (5)

Cited By (10)

Families Citing this family (3)

Family Cites Families (11)

• 1985
  • 1985-03-25 US US06/715,628 patent/US4746327A/en not_active Expired - Fee Related
• 1986
  • 1986-03-18 CA CA000504377A patent/CA1269535A/fr not_active Expired - Fee Related
  • 1986-03-25 EP EP86302199A patent/EP0196217B1/fr not_active Expired - Lifetime
  • 1986-03-25 AT AT86302199T patent/ATE62501T1/de not_active IP Right Cessation
  • 1986-03-25 DE DE8686302199T patent/DE3678597D1/de not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events